Method for forming metal oxide coating film and vapor deposition apparatus

a technology of metal oxide coating film and vapor deposition apparatus, which is applied in the direction of catalyst activation/preparation, physical/chemical process catalysts, coatings, etc., can solve the problem of inability to control the hydrolysis reaction in the gas phase, and achieve the improvement of the utilization factor of ticl4, uniform thickness, and good appearance

Inactive Publication Date: 2007-03-08
OSAKA TITANIUM TECHNOLOGIES
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  • Claims
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AI Technical Summary

Benefits of technology

[0012] The present inventors investigated the above-described CVD film formation method from the new point of view that the progress of a reaction of TiCl4 and H2O in the gas phase is suppressed by controlling contact of TiCl4 vapor supplied as a reactant with water vapor. As a result, it was found that injection of jetted streams of both the TiCl4 vapor and the water vapor through respective nozzles makes it possible to control the time at which these two vapors are allowed to contact and mix, which in turn makes it possible to control within a proper range the time elapsed from mixing of the two vapors until the mixed vapors contact a substrate, thereby significantly preventing a reaction between TiCl4 and H2O from proceeding in the gas phase and leading to elimination of the above-described problems.
[0013] Specifically, by bringing TiCl4 vapor into contact with a substrate within 3 seconds and preferably within one second from its mixing with water vapor, the occurrence of a hydrolysis reaction of TiCl4 in locations other than at the surface of the substrate can be suppressed. Thus, a significant improvement in the rate of film formation and in the utilization factor of TiCl4 for film formation is achieved, and it is made possible to form a titanium oxide film having a uniform thickness and good appearance.
[0014] Although the reason for this has not been elucidated completely, it is thought that due to limitation of the time from contact and mixing of the two vapors by collision before they reach the substrate as described above, the two vapors may arrive at the surface of the substrate while they are mixed only on a macroscopic scale but not completely mixed on a microscopic scale (hence, such that a reaction between TiCl4 and H2O is suppressed). It is also conceivable that the possibility of TiCl4 vapor contacting the substrate is increased, which contributes to an improved rate of film formation.

Problems solved by technology

In the formation of a titanium oxide film by the CVD technique using hydrolysis of TiCl4, a very high reactivity between TiCl4 vapor and water vapor allows the TiCl4 vapor to prematurely react with the water vapor in the gas phase (namely, in the gas space within a vapor deposition chamber) before it reaches a substrate, which causes the above-described various problems.
As a result, TiCl4 vapor fed into the vapor deposition chamber immediately reacted with water vapor which existed in its surroundings, and a hydrolysis reaction in the gas phase could not be controlled.

Method used

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  • Method for forming metal oxide coating film and vapor deposition apparatus
  • Method for forming metal oxide coating film and vapor deposition apparatus

Examples

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example 1

[0055] A quartz plate used as a substrate was placed at an angle of 20° with respect to the horizontal in a quartz tube which was disposed horizontally. At one end of the quartz tube, TiCl4 vapor and water vapor used as reactants for vapor deposition were injected through respective single-orifice nozzles to form jetted streams of vapor and were discharged from the other end of the tube to perform a vapor deposition test.

[0056] The TiCl4 vapor and the water vapor were diluted with argon and dry air, respectively, to form each into a diluted vapor having a concentration of 3%, which was used for injection. The atmosphere in the tube before injection of the vapors was an argon atmosphere. The temperature of the substrate was made 180° C. by heating the tube at 180° C. with an external heater. In order to prevent condensation of the TiCl4 vapor and the water vapor, each diluted vapor was heated by heating its feed pipe to the inlet of the quartz tube at 60° C. The two nozzles were til...

example 2

[0061] Vapor deposition and calcination were carried out in accordance with the procedure in Example 1 except for the following points. In this example, the position of the substrate in the quartz tube was fixed such that the time elapsed from mixing of the TiCl4 vapor and water vapor until contact of the mixed vapors with the substrate was 2 seconds, while the temperature of the substrate was varied in the range of from 100-500° C. The temperature of the substrate was controlled at a predetermined temperature by heating the quartz tube from the outside in an electric oven. For the same purpose as described in Example 1, the feed pipe of each diluted vapor to the inlet of the quartz tube was heated at 60° C. or higher.

[0062] The photocatalytic activity of each titanium oxide film formed on the substrate was evaluated by the aldehyde decomposition test described below. In addition, the adhesion of the titanium oxide film was tested by a tape peel test and evaluated as follows: mark ...

example 3

[0065] Vapor deposition and calcination were carried out in the same manner as in Example 2 except for the following points. In this example, the temperature of the substrate was 180° C., which was the same as in Example 1, but the ratio of TiCl4 vapor to water vapor injected into the quartz tube (H2O / TiCl4 molar ratio) was varied.

[0066] The rate of film formation and the photocatalytic activity of each titanium oxide film formed on the substrate were evaluated as described in Examples 1 and 2, respectively, and the results are shown in Table 3.

TABLE 3Rate of aldehydeRate of filmH2O / TiCl4decompositionformationmolar ratio[ppm / min][nm / min]0.10.79500.51.9520011.561502113030.8511050.7975100.8350

[0067] As can be seen from Table 3, at a H2O / TiCl4 molar ratio of 5 or greater, the rate of film formation decreased. In view of the rate of film formation and the photocatalytic activity, the molar ratio is preferably 3 or lower, and in particular, at a molar ratio of about 0.5, both the rate...

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Abstract

A photocatalytic composite material having a photocatalytic titanium oxide film on the surface of a substrate is produced by a CVD method in which TiCl4 vapor is reacted with water vapor. The TiCl4 vapor and the water vapor are injected into a vapor deposition chamber (9) through nozzles (5) and (6), respectively, such that the resulting two injected vapor streams meet before reaching the substrate, thereby mixing the two vapors. Within 3 seconds after this mixing, the mixed vapors are brought into contact with a substrate (1) which is moving in one direction. Preferably the TiCl4 vapor is injected in a reverse direction with respect to the direction of movement of the substrate through a multi-orifice nozzle (5), while the water vapor is injected through a slit nozzle (6) disposed at a smaller angle with respect to the substrate.

Description

TECHNICAL FIELD [0001] This invention relates to a process for forming a metal oxide film such as a titanium oxide film having a photocatalytic activity on the surface of a substrate by the CVD (chemical vapor deposition) technique, and to a vapor deposition apparatus which is suitable for use in this film forming process. BACKGROUND ART [0002] The photocatalytic activity exhibited by titanium oxide has attracted attention in that it is effective for various environmental depollution treatments including deodorization, prevention of microbial growth, and prevention of fouling. In order to allow the photocatalytic activity of titanium oxide to be exerted, photocatalytic titanium oxide composite materials have been developed in which a film of a photocatalytic titanium oxide is formed on the surface of a substrate selected from a wide variety of materials. [0003] Practical methods for the formation of a titanium oxide film for use as a photocatalyst are roughly classified into an appl...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C23C16/00C01B13/14B01J21/06B01J35/00B01J35/02B01J37/02C01G23/04C01G23/07C23C16/40C23C16/44C23C16/455C23C16/54C23C16/56
CPCB01J21/06B01J21/063B01J35/004B01J37/0238C23C16/545C23C16/405C23C16/455C23C16/45502C23C16/45568C01G23/07
Inventor SHIMOSAKI, SHINJIOGASAWARA, TADASHINAGAOKA, SADANOBUMASAKI, YASUHIRO
Owner OSAKA TITANIUM TECHNOLOGIES
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